CN113061249B - Preparation method of polyethyleneimine - Google Patents
Preparation method of polyethyleneimine Download PDFInfo
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- CN113061249B CN113061249B CN202110471948.5A CN202110471948A CN113061249B CN 113061249 B CN113061249 B CN 113061249B CN 202110471948 A CN202110471948 A CN 202110471948A CN 113061249 B CN113061249 B CN 113061249B
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- polyethyleneimine
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
- C08G73/0213—Preparatory process
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
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Abstract
The invention discloses a preparation method of polyethyleneimine, which comprises the following steps: heating raw materials comprising dibromoethane, tri (2-aminoethyl) amine and N, N-dimethylformamide to react under a closed condition to prepare polyethyleneimine. The method takes dibromoethane and tri (2-aminoethyl) amine as reaction raw materials, carries out nucleophilic substitution and one-step condensation polymerization to obtain polyethyleneimine, uses the tri (2-aminoethyl) amine as an amine compound of a dimer, and has the advantages that the reaction process needs to be carried out in the presence of N, N-dimethylformamide as a solvent, and under the condition of not adding N, N-dimethylformamide as a solvent, two reactants of dibromoethane and tri (2-aminoethyl) amine react to easily generate paste to be hardened and cannot be stirred for reaction. The preparation method provided by the invention avoids the traditional mode of synthesizing the polyethyleneimine monomer which is high in pollution and has certain hazard, and provides a new thought and method for green and efficient synthesis of polyethyleneimine.
Description
Technical Field
The invention relates to the technical field of polymer organic synthesis, in particular to a preparation method of polyethyleneimine.
Background
Polyethyleneimine (PEI) is a copolymer of- (CH)2CH2NH)nThe PEI is a cationic polymer with extremely high charge density and is also the largest cationic polymer known at present, because PEI is rich in primary amine, secondary amine and tertiary amine groups on the molecular structure, and isolated electrons on nitrogen have an attraction effect on cations in a solution.
For the preparation of PEI, the subsequent polymerization is carried out after the preparation of the ethyleneimine monomer in industry. Ethyleneimine is a highly reactive, corrosive and toxic intermediate. Can be synthesized according to different methods. The traditional method for synthesizing polyethyleneimine from an initial compound of polyethyleneimine must deal with highly reactive, toxic and corrosive monomers of polyethyleneimine, and must ensure that the polyethyleneimine cannot be retained in products and waste water materials, so that the traditional method has extremely high environmental pollution and certain human hazard.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of polyethyleneimine, which is realized by a method of heating and polymerizing dibromoethane and tri (2-aminoethyl) amine in N, N-dimethylformamide without using the polyethyleneimine.
In a first aspect of the present invention, a method for preparing polyethyleneimine is provided, comprising the following steps:
heating raw materials comprising dibromoethane, tri (2-aminoethyl) amine and N, N-dimethylformamide to react under a closed condition to prepare polyethyleneimine.
The preparation method of the polyethyleneimine provided by the embodiment of the invention has at least the following beneficial effects:
the invention takes dibromoethane and tri (2-aminoethyl) amine as reaction raw materials, and prepares Polyethyleneimine (PEI) by one-step condensation polymerization through nucleophilic substitution according to the following reaction formula:
the tri (2-aminoethyl) amine is used as an amine compound of a trimer, the tri (2-aminoethyl) amine has a longer chain segment which can ensure that the tri (2-aminoethyl) amine is not easy to form a closed six-membered ring, namely a byproduct piperazine, with dibromoethane under the reaction, in addition, the reaction process needs to be carried out in the presence of a solvent N, N-dimethylformamide, and the N, N-dimethylformamide has the functions of dissolving the tri (2-aminoethyl) amine and keeping the reaction mild and uniform contact, and under the condition of not adding an N, N-dimethylformamide solvent, the reaction of two reactants of dibromoethane and tri (2-aminoethyl) amine is easy to generate paste hardening and cannot be stirred for reaction. The preparation method provided by the invention avoids the traditional mode of synthesizing the polyethyleneimine monomer which is high in pollution and has certain hazard, and provides a new thought and method for green and efficient synthesis of polyethyleneimine.
In some embodiments of the invention, the polyethyleneimine has a viscosity of 9851 to 5421.7mPa · s.
In some embodiments of the invention, the weight average molecular weight of the polyethyleneimine is 1100 to 1600.
In some embodiments of the invention, the volume of the N, N-dimethylformamide is: the volume ratio of dibromoethane to tris (2-aminoethyl) amine is 2-3: 1.
in some embodiments of the invention, the temperature of the heating reaction is 57-150 ℃; preferably, the temperature of the heating reaction is 70-80 ℃.
In some embodiments of the invention, the heating reaction time is 72h and more.
In some embodiments of the invention, the heating reaction is carried out in an inert gas atmosphere.
In some embodiments of the invention, the inert gas is nitrogen.
In some embodiments of the invention, the heating reaction is carried out under stirring conditions, with a stirring speed of 300rpm or more.
In some embodiments of the invention, the dibromoethane is at least 60% pure and the tris (2-aminoethyl) amine is at least 60% pure.
In some embodiments of the invention, the molar ratio of dibromoethane: tris (2-aminoethyl) amine ≤ 1 eq: 1 eq. In further embodiments of the invention, the molar ratio of dibromoethane: tris (2-aminoethyl) amine ═ 1 eq: 1 eq. The excessive addition of the tris (2-aminoethyl) amine helps to ensure the presence of the terminal primary amine content of the polyethyleneimine formed, but also leads to a high residual amount of tris (2-aminoethyl) amine, which requires further removal of impurities, ideally using the stoichiometric equivalent of 1: 1 dibromoethane and tri (2-aminoethyl) amine.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a graph of shear viscosity η versus shear rate γ for commercial PEI;
FIG. 2 is a plot of viscosity versus molecular weight for commercially available PEI's calibrated by the viscosity method;
FIG. 3 is a graph showing the change in shear viscosity eta versus shear rate gamma of the products prepared in examples 1 to 3 of the present invention;
FIG. 4 is a comparison of IR spectra of products prepared in examples 1-3 of the present invention and commercial PEI;
FIG. 5 is a diagram showing the products obtained in examples 1 to 3 of the present invention13A C NMR spectrum;
FIG. 6 is a pictorial representation of a product prepared in examples 1-3 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The instrument that viscosity survey used in this application is Anton Paar rotational rheometer, and the model is MCR 302, and the test method is the viscosity curve, and concrete survey process is: changing the shear rate, recording the change curves of the shear viscosity eta and the shear stress tau, setting the dynamic shear rate gamma to be 0.01-200(1/s), recording the viscosity of the first newtonian region, namely the required viscosity, and measuring the viscosity curve by using the commercially available Polyethyleneimine (PEI) with known molecular weight as shown in fig. 1.
The molecular weight measurements in the following examples were carried out using viscosity calibration using commercially available Polyethylenimine (PEI) of known molecular weight to obtain a fitted curve relating molecular weight: 1.88142 · lgMw-2.05469 ═ lg η (Mw is the weight average molecular mass, η is the viscosity), and then the molecular weight can be obtained by measuring the viscosity of the product concerned and substituting into the calculation, and the fitted curve is shown in fig. 2. The commercial PEI used above was a Michael product with a content of 99% and above.
The amine value is calculated according to the method of the literature (von Harpe, A., et al. (2000). "chromatography of commercial available and synthesized polyethylene for gene delivery", "Journal of Controlled Release 69(2):309-13C NMR spectrum is calculated.
Example 1
This example provides a polyethyleneimine prepared according to the following steps:
0.30mol of dibromoethane (56.358g) and 0.30mol of tris (2-aminoethyl) amine (43.869g) were added in this order under a nitrogen atmosphere to a 500mL steel-made closed autoclave, 300mL of N, dimethylformamide were added, the autoclave was heated to 150 ℃ under a nitrogen pressure of 1 bar, mechanically stirred at this temperature and at a rotational speed of 300rpm and held for 72 h. The obtained product is transferred into a rotary evaporator to remove N, N-dimethylformamide and dibromoethane.
FIG. 3 shows the shear viscosity η and the amine value of the product obtained in this example measured according to the shear viscosity η and the shear rate γ of the product obtained in this example 1, which are shown in Table 1, and then substituted into the standard viscosity curve, so that the viscosity of the product obtained in this example is 9851mPa · s, and the weight average molecular weight Mw is 1637 g/mol.
FIG. 4 shows a comparison of the IR spectra of the product of example 1 and commercial PEI, from which it can be seen that the product of this example shows a more desirable peak position and related important signal peaks are analyzed, the most important characteristic peaks being: the in-plane bending vibration of N-H primary amine has a signal peak at 1650--1 Performing the following steps; C-H bending vibration, signal peak 1465--1 Performing the following steps; secondary amine C-N stretching vibration, signal peak 1190--1 Performing the following steps; primary amine C-N stretching vibration, signal peak at 1120--1 Performing the following steps; wherein the other vibration of N-H is at 900-700cm-1 The detection error is large, and the judgment is not carried out. The experimental results show that the main signal peaks of the product prepared in this example are consistent with those of the commercial PEI product, and a small amount of impurities are present, indicating that the product prepared in this example 1The product obtained is polyethyleneimine.
FIG. 5 shows the product prepared in example 113C NMR spectra and the carbon spectral peak positions of polyethyleneimine are shown in von Harpe, A., et al (2000), "chromatography of commercially available and synthesized polyethylene for gene delivery," Journal of Controlled Release 69(2):309 and 322, which further proves that the product prepared in example 1 of the present invention is polyethyleneimine.
Example 2
This example provides a polyethyleneimine prepared according to the following steps:
0.30mol of dibromoethane (56.358g) and 0.30mol of tris (2-aminoethyl) amine (43.869g) were added in this order under a nitrogen atmosphere to a 500mL steel-made closed autoclave, 300mL of N, dimethylformamide were added, the autoclave was heated to 100 ℃ under a nitrogen pressure of 1 bar, mechanically stirred at this temperature and at a rotational speed of 300rpm and held for 72 h. The obtained product is transferred into a rotary evaporator to remove N, N-dimethylformamide and dibromoethane.
FIG. 3 shows the shear viscosity eta versus shear rate gamma curve of the product of example 2, and the viscosity and amine value of the product obtained in this example are measured, and the results are shown in Table 1, and then the standard viscosity curve is substituted, so that the viscosity of the product obtained in this example is 9722.3 mPas, and the weight average molecular weight Mw is 1625 g/mol.
FIG. 4 shows a comparison of the IR spectra of the product of example 2 and commercial PEI, from which it can be seen that the product prepared in example 2 is polyethyleneimine.
Of the product obtained in this example13The C NMR spectrum is shown in FIG. 5, which confirms that the product obtained in example 2 of the present invention is polyethyleneimine.
Example 3
The examples provide a polyethyleneimine prepared according to the following steps:
0.30mol of dibromoethane (56.358g) and 0.30mol of tris (2-aminoethyl) amine (43.869g) were added in this order under a nitrogen atmosphere to a 500mL steel-made closed autoclave, 300mL of N, dimethylformamide were added, the autoclave was heated to 80 ℃ under a nitrogen pressure of 1 bar, mechanically stirred at this temperature and at a rotational speed of 300rpm and held for 72 h. The obtained product is transferred into a rotary evaporator to remove N, N-dimethylformamide and dibromoethane.
FIG. 3 shows the variation curve of shear viscosity eta and shear rate gamma of the product of example 3, the viscosity and amine value of the product obtained in this example are measured, and the results are shown in Table 1, and then the results are substituted into the standard viscosity curve, so that the viscosity of the product obtained in this example is 5421.7mPa & s, and the weight average molecular weight Mw is 1191 g/mol.
FIG. 4 shows a comparison of the IR spectra of the product of example 3 and commercial PEI, from which analysis shows that the product of example 2 is polyethyleneimine.
Of the product obtained in this example13The C NMR spectrum is shown in FIG. 5, which confirms that the product obtained in example 3 of the present invention is polyethyleneimine.
FIG. 6 is a photograph showing real objects of the products obtained in examples 1 to 3, and it can be seen that the products obtained in examples 1 to 3 have uniform colors.
TABLE 1 parameters for the products prepared in examples 1-3
As can be seen from Table 1, the viscosity of the polyethyleneimine prepared in the examples of the present invention is in the range of 9851 to 5421.7 mPas, the weight average molecular weight Mw is in the range of 1100 to 1600, and the monomer structure of the polyethyleneimine is-CH2CH2The NH-, C/N atomic ratio of 2 is a state which is peculiar to the ideal product, and it can be seen from the table that the product obtained by the example of the present invention is close to the ideal state. In addition, the polyethyleneimine has certain requirements on amine values (different amine contents) in practical use, and the polyethyleneimine can be obtained by controlling reaction conditionsThe polyethyleneimine with different amine values meets the requirements of different amine values.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (11)
1. A preparation method of polyethyleneimine is characterized by comprising the following steps:
heating raw materials comprising dibromoethane, tri (2-aminoethyl) amine and N, N-dimethylformamide to react under a closed condition to prepare polyethyleneimine; the temperature of the heating reaction is 57-150 ℃.
2. The method for producing polyethyleneimine according to claim 1, wherein the viscosity of polyethyleneimine is 9851 to 5421.7 mPa-s.
3. The method for producing polyethyleneimine according to claim 1, wherein the weight-average molecular weight of the polyethyleneimine is 1100 to 1600.
4. The method for producing polyethyleneimine according to claim 1, wherein the volume of N, N-dimethylformamide is: the volume ratio of dibromoethane to tris (2-aminoethyl) amine is 2-3: 1.
5. the method for producing polyethyleneimine according to claim 1, wherein the temperature of the heating reaction is 70 to 80 ℃.
6. The method for producing polyethyleneimine according to claim 1, wherein the heating reaction time is 72 hours or more.
7. The method for producing polyethyleneimine according to any one of claims 1 to 6, wherein the heating reaction is performed in an inert gas atmosphere.
8. The method for producing polyethyleneimine according to claim 7, wherein the inert gas is nitrogen.
9. The process for producing polyethyleneimine according to any one of claims 1 to 6, wherein the purity of dibromoethane is 60% or more, and the purity of tris (2-aminoethyl) amine is 60% or more.
10. The process for producing polyethyleneimine according to any one of claims 1 to 6, wherein the molar ratio of dibromoethane: tris (2-aminoethyl) amine ≤ 1 eq: 1 eq.
11. The method for producing polyethyleneimine according to claim 10, wherein the molar ratio of dibromoethane: tris (2-aminoethyl) amine =1 eq: 1 eq.
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